Reaction products of primary fatty amines and ketose sugars



United States Patent C) REACTION PRODUCTS F PRllVIARY FATTY AMINES ANDKETOSE SUGARS John G. Erickson, Minneapolis, Minn., assignor to GeneralMills, Inc., a corporation of Delaware N 0 Drawing. Application November26, 1952, Serial No. 322,812

6 Claims. (Cl. 260-211) The present invention relates to new compoundsobtained by the reaction of fatty amines with ketose sugars and to theprocess of producing these compounds. These compounds contain a minimumof two fatty amino groups per molecule and may contain a number of fattyamino groups equivalent to the number of carbon atoms in the ketosesugar. The compounds vary in their properties with the number of fattyamine groups. The lower members of the group (those containing 2 or 3fatty amino groups per molecule) can be used directly as surface activeagents or may be converted into other surface active agents by suitablereactions, such as sulfation, hydrogenation and the like. The compoundscontaining larger numbers of fatty amino groups may be used towaterproof textiles, either by direct deposition on the fabric or byreaction with formaldehyde and subsequent insolubilization on the cloth.

It is, therefore, an object of the present invention to provide novelreaction products of fatty amines and ketose sugars in which thecompounds contain at least two fatty amino groups per molecule.

It is another object of the present invention to provide a process ofproducing such compounds.

The invention is applicable to ketopentoses, ketohexoses andketoheptoses. Suitable sugars which may be used in the present inventioninclude fructose, sorbose, tagatose, psicose, xyloketose, riboketose,sedoheptose, mannoketoheptose, perseulose and glucoheptulose. By meansof the present invention it is possible to introduce a fatty amino grouponto each carbon atom of the ketose sugar.

The fatty amines which may be used include the primary amines, eithersaturated or unsaturated, containing from 8-22 carbon atoms. These maybe single, isolated amines, or may be mixed amines derived from thefatty acids of a fat or oil, or from any selected group of such fattyacids.

In preparing these products it is desirable to use an excess of amineover the theoretical quantity of amine required to introduce the desirednumber of fatty amino groups into the sugar. The introduction of twofatty groups into the molecule may be attained even without theemployment of an excess of amine. For example, octadecylamine andfructose in equimolar quantities yield the dioctadecylamino fructosecompound merely upon allowing the mixture to stand at room temperaturefor 24 hours. However, even in this instance it is preferred to use aratio of at least 2 mols of amine to 1 of sugar. Where it is desired tointroduce higher numbers of fatty amine groups, it is preferred to usestill higher ratios of amine to sugar; for example, as high as 8 to 10mols of amine per mol of sugar where it is desired to introduce 5 or 6fatty amino groups.

Room temperature is satisfactory for the introduction of two fatty aminogroups into the sugar molecule. In order to obtain more highlysubstituted products it is preferred to heat the reactants together attemperatures within the range of 30-100 C. Temperatures in excessPatented Dec. 3, 1957 of C. tend toward excessive decomposition. Thepreferred temperature range is 50-80 C. The time required depends uponthe temperature used and the product desired. For example, from lO-20hours are suflicient at room temperature to introduce 2 fatty aminogroups. To introduce 3 or 4 fatty amino groups requires more drasticconditions. To introduce 6 fatty amino groups into fructose, forexample, may require from 4-6 hours at 70 C.

The reaction is preferably carried out in the presence of an aqueoussolvent such as a mixture of water and a lower aliphatic alcohol.Alcohols such as methyl, ethyl, propyl, isopropyl and the like aresuited for this purpose.

There are numerous possibilities for the structure of these compoundsand for the course which the reaction takes. The following reactionsindicate the courses which the reaction may take and the products whichmay be obtained.

anion anion ano CH=YNR i=0 (|J=NR OHNHR CHNHR anon RNH: anon anon RNH,anon anon anon anon V anon anon anon anon anon CHZOH OHzOH CHzOH 0112011OHZNHR anmnn OHZNHR CIEHNHR anNnR CHNHR a=o RNH: G=NR CHNHR n A} nonanon =0 anon anon anon angon anzon anion anion anion anzon (IJHNHR anNnRanNnR a=o RNn. C=NR CHNHR I anon anon =0 anon anon anon anion CHzOHanion These reactions may continue until all oxygen in the sugar hasbeen replaced by nitrogen. Obviously, a large number of differentcompounds is possible. Not only the straight-chain forms shown above canbe formed, but also others such as:

OH OH CHzOH CHzNHR CHNHR CIHENHR CHNHR OHNHR HrNHR JHNHR CHNHR JHNHR andCHNHR C IHNHR i=0 CHNHR CH=NR (IJHZOH CH=NR Besides these straight-chainforms, one can get their cyclized forms. Some of these are:

RNHCH CH2 CH RNHCH RNHC H RNHJJH RNBI IH O, RNHC I'H O, RNEK JH 0, etc.RNHC JH RNHCH RNHCH HC- RNHC HOC I HzOH H2015 JHzOH Example 1 A solutionof 5.4 parts 'of fructose and 11.1 parts of dodecylamine in a mixture ofequal volumes of water and isopropyl alcohol was allowed to stand atroom temperature for days. 'It was then filtered and the reactionproduct was recrystallized from a low-boiling paraflin hydrocarbon. Thepure product melts with decomposition at 103.5-104.5 C. Analysis showedthat it had been formed by the reaction of 2 mols of dodecylamine with 1mol of fructose.

Example 2 A solution of 26.9 parts of octadecylamine and 18 parts offructose in a mixture of two volumes of isopropyl alcohol and one volumeof water was allowed to stand at room temperature for two days. Themixture was filtered, giving a crude product. After tworecrystallizations from alcohol and ethyl acetate, it melted withdecomposition at 1052-106 C. Analysis showed that it had been formed bythe reaction of two mols of amine for each mol of sugar.

Example 3 A solution of 26.9 parts of octadecylamine and 2.70 parts ofsorbose in a mixture of 4 volumes of isopropyl alcohol and 1 volume ofwater was heated to 60-70 once on each of 26 days, then allowed to cool.It was filtered and the product was recrystallized from alcohol, M. P.63.56S C. Analysis showed that between 4 and 5 mols of amine had reactedwith each mol of sugar.

Example 5 A mixture of 3 parts of the reaction product of Example 4 and3 parts of octadecylamine in benzene was heated at 80 C. for 6 hours,cooled and filtered. Evaporation of the filtrate, followed byrecrystallization of the residue from alcohol, gave a product, M. P. 67-69.5 C. Analysis showed that it had been formed by reaction of 5 mols ofamine with 1 of sugar.

Example 6 Four parts of the reaction product of Example 4 and 4 parts ofoctadecylamine were dissolved in isopropyl alcohol. The mixture washeated two hours at 80 C., cooled and filtered. Recrystallization from amethanolisopropyl alcohol mixture gave a product, M. P. 65- 67 C.Analysis showed that between 5 and 6 mols of amine had reacted for eachmol of sugar.

Other ketone sugars containing 5-7 carbon atoms may be substituted forthe sugars disclosed in the examples with similar results.

I claim as my invention:

1. A ketose sugar-fatty amine reaction product, the ketose sugarcontaining from 5-7 carbon atoms, the fatty amine containing from 12-18carbon atoms and the reaction product containing a number of fatty aminogroups varying from 2 to the number of carbon atoms in the ketone sugar.

2. A fructose-fatty amine reaction product, the fatty amine containingfrom 12-18 carbon atoms and the reaction product containing from 2-6fatty amino groups.

3. A sorbose-fatty amine reaction product, the fatty amine containingfrom 12-18 carbon atoms and the reaction product containing from 2-6fatty amino groups.

4. Process of preparing ketose-fatty amine reaction products containingat least 2 fatty amino groups which comprises reacting a ketosecontaining from S-7 carbon atoms with a fatty amine containing from12-18 carbon atoms, the fatty amine being employed in excess of thetheoretical quantity required for the introduction of the desired numberof fatty amino groups, at a temperature within the range of 40 to 100 C.

5. Process of producing ketose-fatty amine reaction products whichcomprises reacting a ketose containing from 5-7 carbon atoms with afatty amine containing from 12-18 carbon atoms in the range of to C. inthe presence of at least 2 mols of amine per mol of ketose.

6. Process of producing ketose-fatty amine reaction products whichcomprises reacting a ketose containing from 5-7 carbon atoms with afatty amine containing from 12-18 carbon atoms, the fatty amine beingemployed in a molar ratio at least 3 times that of the ketose at atemperature within the approximate range of 50- References Cited in thefile of this patent UNITED STATES PATENTS 2,016,962 Flint et al. Oct. 8,1935 2,016,956 Calcott et al. Oct. 8, 1935 2,181,929 Werntz Dec. 5, 1939FOREIGN PATENTS 519,381 Great Britain Mar. 26, 1940 OTHER REFERENCESVotocek et al.: Collection Trav. Chim. Tckecoslovaquie, vol. 6 (1934),pp. 77-96. (Pages 93-5 relied upon.) (Copy in the Bureau of GeologicalSurvey Library.)

Mitts et al.: J. A. C. S., 66, 483 (1944).

Mitts et al.: J. A. C. 8., vol. 66, PP. 483-6 (1944).

Erickson: J. A. C. 8., vol. 77, page 2840 (1955).

1.A KETOSE SUGAR-FATTY AMINE REACTION PRODUCT, THE KETOSE SUGER CONTAINING FROM 5-7 CARBON ATOMS, THE FATTY AMINE CONTAINING FROM 12-18 CARBON ATOMS AND THE REACTION PRODUCT CONTAINING A NUMBR OF FATTY AMINO GROUPS VARYING FROM 2 TO THE NUMBER OF CARBON ATOMS IN THEEKETONE SUGAR.
 4. PROCESS OF PREPARING KETOSE-FATTY AMINE REACTION PRODUCTS CONTAINING AT LEAST 2 FATTY AMINO GROUPS WHICH COMPRISES REACTING A KETOSE CONTAINING FROM 5-7 CARBON ATOMS WITH A FATTY AMINE CONTAINING FROM 12-18 CARBON ATOMS WITH FATTY AMINE BEING EMPLOYED IN EXCESS OF THE THEORETICAL QUANTITY REQUIRED FOR THE INTRODUCTION OF THE DESIRED NUMBER OF GATTY AMINO GROUPS, AT A TEMPERATURE WITHIN THE RANGE IF 40 TO 100* C. 